A photo-induced Minisci–type cyanoalkylation of azauracils was developed under metal-free and base-free conditions. Readily available cyclobutanone oxime esters were used as the cyanoalkylating reagents via C-C bond cleavage to generate the γ-cyanoalkyl azauracil derivatives in good to moderate yields. The introduced cyano group can be easily converted into many other functional groups, thus makes current protocol more practical.